CN104549325B - Catalyst for preparing low-carbon olefin from synthesis gas by one-step method, preparation method and application of catalyst - Google Patents
Catalyst for preparing low-carbon olefin from synthesis gas by one-step method, preparation method and application of catalyst Download PDFInfo
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Abstract
The invention relates to a catalyst for preparing low-carbon olefin from synthesis gas by a one-step method and a preparation method of the catalyst, which are mainly used for solving the problems of low CO conversion rate and low selectivity of low-carbon olefin in the reaction for preparing low-carbon olefin from synthesis gas in the prior art. The catalyst adopted by the invention comprises the following components in percentage by weight: (a) 5-60% of ferrum element or an oxide of the ferrum element; (b) 1-10% of cobalt element or an oxide thereof; (c) 4-20% of at least one element or an oxide thereof selected from strontium or magnesium; (d) 4-20% of at least one element or an oxide thereof selected from molybdenum and zirconium; (e) 1-10% of erbium element or an oxide thereof; and (f) 30-85% of a cocoanut active charcoal carrier. By adopting the technical scheme, the problem is solved well, and the catalyst and the preparation method thereof can be applied to the industrial production for preparing the low-carbon olefin from synthesis gas by using a fixed bed.
Description
Technical field
The present invention relates to a kind of catalyst of one-step method from syngas producing light olefins, the preparation method of catalyst and its use
On the way.
Background technology
Low-carbon alkene refers to that carbon number is less than or equal to 4 alkene.Low-carbon alkene right and wrong with ethene, propylene as representative
Often important basic organic chemical industry raw material, with the rapid growth of China's economy, for a long time, low-carbon alkene market is not for should
Ask.At present, the production of low-carbon alkene mainly adopts lighter hydrocarbons（Ethane, naphtha, light diesel fuel）The petrochemical industry route of cracking, due to
The day by day shortage of Global Oil resource and the long-term run at high level of crude oil price, development low-carbon alkene industry relies solely on petroleum light hydrocarbon
Tube cracking furnace technique for raw material can run into an increasing raw material difficult problem, and low-carbon alkene production technology and raw material must be polynary
Change.The direct preparing low-carbon olefins of one-step method from syngas be exactly carbon monoxide and hydrogen under catalyst action, anti-by F- T synthesis
Process that carbon number be less than or equal to 4 low-carbon alkene should be directly obtained, this technique need not be from conjunction as indirect method technique
Become gas through methyl alcohol or dimethyl ether, prepare alkene, simplification of flowsheet further, greatly reduce investment.Petroleum resources are short at home
Lack, it is current that external dependence degree more and more higher, international oil price constantly rise violently, and can widen former material from synthesis gas producing olefinic hydrocarbons technique
Material source, will produce synthesis gas with crude oil, natural gas, coal and recyclable materials for raw material, can be based on high cost raw material
Replacement scheme is provided in terms of the steam cracking technology of naphtha.The abundant coal resources of China and the coal price of relative moderate
It is that Development of Coal is refined oil and application preparation of low carbon olefines by synthetic gas technique provides the good market opportunity.And enrich in Natural Gas In China
Oil gas field near, if Gas Prices are cheap, be also application preparation of low carbon olefines by synthetic gas technique fabulous opportunity.If energy
Using coal and the natural gas resource of China's abundant, by gas making producing synthesis gas（Carbon monoxide and the gaseous mixture of hydrogen）, send out
The substitute energy source for petroleum technology of exhibition preparation of low carbon olefines by synthetic gas, will be significant to solving energy problem of China.
One-step method from syngas producing light olefins technology originates from traditional Fischer-Tropsch synthesis, traditional Fischer-Tropsch synthetic
Carbon number distribution defer to ASF distribution, each hydro carbons all has theoretical maximum selectively, such as C2-C4The selectivity of cut is up to
57%, gasoline fraction (C5-C11) selectivity be up to 48%.Chain growth probability α value is bigger, and the selectivity of product heavy hydrocarbon is got over
Greatly.Once α value determines, the selectivity of whole synthetic product determines that, chain increase probability α value depend on catalyst form,
Granularity and reaction condition etc..In recent years it has been found that due to alhpa olefin on a catalyst adsorb the alkene secondary counter causing again
Should, product distribution deviates from preferable ASF distribution.F- T synthesis are a kind of strong exothermal reactions, and substantial amounts of reaction heat will promote catalyst
Carbon deposit reaction is easier to generate methane and low-carbon alkanes, leads to selectivity of light olefin significantly to decline；Secondly, complicated power
It is unfavorable that factor also causes to selectivity synthesis low-carbon alkene；The ASF distribution of Fischer-Tropsch synthetic limits synthesizing low-carbon alkene
Selectivity.The catalyst of F- T synthesis gas producing light olefins is mainly iron catalyst series, directly makes to improve synthesis gas
Take the selectivity of low-carbon alkene, physics and chemical modification can be carried out to fischer-tropsch synthetic catalyst, as suitable using molecular sieve
Pore passage structure, is conducive to low-carbon alkene to diffuse out metal active centres, the secondary response of suppression low-carbon alkene in time；Improve gold
Belong to ion dispersiveness, also have preferable olefine selective；Support-metal strong interaction changes and can also improve low-carbon alkene choosing
Selecting property；Add suitable transition metal, the bond energy of active component and carbon can be strengthened, suppression methane generates, and improves low-carbon alkene
Selectively；Add electronics accelerating auxiliaries, promote CO chemisorbed heat to increase, adsorbance also increases, and hydrogen adsorptive capacity reduces, result
Selectivity of light olefin increases；Eliminate catalyst acid center, the secondary response of low-carbon alkene can be suppressed, improve it selectively.
By the Support effect of catalyst carrier and some transition metal promoter of interpolation and alkali metal promoter, can obviously improve catalyst performance
Can, develop the fischer-tropsch synthetic catalyst of the novel high-activity high selectivity producing light olefins with product non-ASF distribution.
One-step method from syngas is directly produced low-carbon alkene, it has also become one of study hotspot of fischer-tropsch synthetic catalyst exploitation.
In patent CN1083415A disclosed in Dalian Chemiclophysics Inst., Chinese Academy of Sciences, with the Group IIA alkali metal oxide such as MgO or high silicon
Zeolite molecular sieve（Or phosphorus aluminium zeolite）The iron supporting-Mn catalyst system, makees auxiliary agent with highly basic K or Cs ion, in synthesis gas system
Low-carbon alkene reaction pressure is 1.0 ~ 5.0MPa, at 300 ~ 400 DEG C of reaction temperature, can obtain higher activity（CO conversion ratio
90%）And selectivity（Selectivity of light olefin 66%）.But this catalyst preparation process complexity, particularly carrier zeolite molecular sieve
Preparation shaping process cost is higher, is unfavorable for industrialized production.The number of patent application that Beijing University of Chemical Technology is declared
In 01144691.9, laser pyrolysis processes are adopted to be prepared for reference to solid phase reaction combination technique with Fe3Fe base nano-catalytic based on C
Agent is applied to preparation of low carbon olefines by synthetic gas, and achieves good catalytic effect, due to needing, using laser pyrolysis technology, to prepare
Technics comparing is loaded down with trivial details, and raw material adopts Fe (CO)5, catalyst cost is very high, and industrialization is difficult.It is special that Beijing University of Chemical Technology is declared
In sharp ZL03109585.2, the Fe/ activated-carbon catalyst that manganese, copper, zinc silicon, potassium etc. are auxiliary agent is prepared using vacuum impregnation technology and is used for
Preparation of low carbon olefines by synthetic gas reacts, under conditions of the circulation of no unstripped gas, CO conversion ratio 96%, and low-carbon alkene is in hydrocarbon
In selectivity 68%.The molysite that this catalyst preparation uses and auxiliary agent manganese salt are more expensive and less soluble ferric oxalate and acetic acid
Manganese, simultaneously with ethanol as solvent, the just inevitable cost of material increasing catalyst preparation process and running cost.For further
Reduce the cost of catalyst, in its number of patent application 200710063301.9, catalyst adopts common medicine and reagent system
Standby, the molysite of use is ferric nitrate, and manganese salt is manganese nitrate, and sylvite is potassium carbonate, and activated carbon is coconut husk charcoal, can catalyst must flow
Carry out high-temperature roasting and Passivation Treatment under dynamic nitrogen protection, need special installation, preparation process is complicated, relatively costly.And it is above-mentioned
CO conversion ratio in fixed bed reaction for the catalyst and selectivity of light olefin are all relatively low.
Content of the invention
The technical problem to be solved is that in prior art, synthesis gas produces CO conversion ratio in low-carbon alkene technology
The low problem of selectivity of light olefin in low and product, provides a kind of method of new one-step method from syngas producing light olefins, should
Method uses new fixed bed F- T synthesis producing light olefins iron-cobalt bimetallic catalyst, has low in CO high conversion rate and product
The high advantage of carbene hydrocarbon-selective.
For solving above-mentioned technical problem, the technical solution used in the present invention is as follows：A kind of low for one-step method from syngas system
The catalyst of carbon olefin, includes following components by weight percentage：
A) 5～60% ferro element or its oxide；
B) 1～10% cobalt element or its oxide；
C) 4～20% at least one element in strontium and magnesium or its oxide；
D) 4～20% at least one element in molybdenum and zirconium or its oxide；
E) 1～10% er element or its oxide；
F) 30～85% coconut activated high-area carbon.
In technique scheme, the preferred version of the oxide of iron is di-iron trioxide, by weight percentage content
Preferred scope is 10～50%；The preferred version of the oxide of cobalt is cobaltosic oxide, the preferred model of content by weight percentage
Enclose for 1～5%；The preferred version of the oxide of strontium and magnesium is respectively strontium oxide strontia and magnesia, and content is excellent by weight percentage
Scope is selected to be 5～15%；The preferred version of the oxide of molybdenum and zirconium is respectively molybdenum oxide and zirconium oxide, contains by weight percentage
The preferred scope of amount is 5～15%；The preferred version of the oxide of erbium is oxidation bait, the preferred model of content by weight percentage
Enclose for 1～5%.The preferred version of carrier be coconut activated high-area carbon, by weight percentage the preferred scope of content be 40～
70%.
In technique scheme, the preparation method of one-step method from syngas producing light olefins catalyst used, including following
Step：
（1）Coconut activated high-area carbon water washed for pickling is carried out ultrasonic and dried process, makes carrier H stand-by；
（2）By molysite, cobalt salt, magnesium salts or strontium salt, molybdenum salt or zirconates, and erbium salt, be dissolved in make in water deionized water mixed
Close solution I；
（3）Under the conditions of vacuum 1 ~ 80 kPa, above-mentioned mixed solution I be impregnated in（1）The carrier H handling well in step
Go up to obtain catalyst precarsor J；
（4）By catalyst precarsor J, roasting after drying, obtain required catalyst.
In technique scheme, the preferred scope of the sintering temperature of catalyst precarsor is 450 ~ 750 DEG C, roasting time excellent
Scope is selected to be 1.0 ~ 4.5 hours.
In technique scheme, the method that described synthesis gas produces low-carbon alkene, with synthesis gas as raw material, H2With CO's
Mol ratio be 1 ~ 3, reaction temperature be 250 ~ 400 DEG C, reaction pressure be 1.0 ~ 3.0Mpa, feed gas volume air speed be 500 ~
5000h-1Under conditions of, unstripped gas is generated with described catalyst haptoreaction and contains C2～C4Alkene.
The preprocess method of carrier cocoanut active charcoal is dust technology and deionized water carrying out washing treatment, all for the routine of this area
Preprocess method is in order to remove the impurity of coconut activated carbon surface.
The catalyst that the inventive method adopts is prepared by vacuum impregnation technology, can make active component and auxiliary agent high uniformity
It is scattered in cocoanut active charcoal carrier surface, increases the quantity of the active sites being exposed to carrier surface, improve the conversion ratio of CO.
The inventive method adopt catalyst in introduce Fischer-Tropsch synthesis second active component Co, alkaline-earth metal Sr or
Mg, transition metal M o or Zr, and lanthanide series metal Er is as catalyst promoter, can with the electron valence state of modulation active component Fe,
Thus being conducive to improving the CO conversion ratio of catalyst and the selectivity of low-carbon alkene.Especially it is introduced into the second active component Co and lanthanum
Be metal Er, not only can modulation active component electron valence state, and strengthen catalyst activity component and the phase interaction of carrier
With intensity, thus being conducive to improving the selectivity of light olefin of catalyst.
The reaction condition of one-step method from syngas producing light olefins is as follows：With H2Synthesis gas with CO composition is raw material, H2With
The mol ratio of CO is 1 ~ 3, is 250 ~ 400 DEG C in reaction temperature, and reaction pressure is 1.0 ~ 3.0Mpa, and feed gas volume air speed is
500~5000h-1Under conditions of, unstripped gas is contacted with above-mentioned catalyst.Achieve preferable technique effect：CO conversion ratio up to
99.9%, improve 3.9% than prior art；Selectivity in hydrocarbon for the low-carbon alkene, up to 77.5%, carries than prior art
High by 9.5%, more detailed result sees attached list.
The present invention is described further for the following examples, and protection scope of the present invention is not subject to these embodiments
Restriction.
Specific embodiment
【Embodiment 1】
The cocoanut active charcoal weighing 100.0 gram of 60 ~ 80 mesh carries out dust technology and deionized water carrying out washing treatment, dry at 120 DEG C
It is stand-by that dry 4h makes carrier H；By 101.2 grams of Fe(NO3)39H2Os, 10.9 grams of cabaltous nitrate hexahydrates, 18.4 grams of strontium nitrates, 12.3
Grams four hydration ammonium heptamolybdates, 7.0 gram of five nitric hydrate erbium, are dissolved in 35.0 grams of deionized waters and make mixed solution I；In vacuum
Under conditions of 80kPa, above-mentioned mixed solution I be impregnated on 55.0 grams of coconut activated high-area carbon H having prepared to obtain catalyst
Precursor J；The catalyst precarsor J having impregnated is dried under the conditions of 120 DEG C, then carries out roasting, 600 DEG C of sintering temperature, during roasting
Between 3h, that is, obtain the catalyst of required one-step method from syngas producing light olefins.Prepared catalyst by weight percentage, wraps
Containing following components：20% Fe2O3, 3% Co3O4, 9% SrO, 10% MoO3, 3% Er2O3, 55% C (cocoanut active charcoal, similarly hereinafter)；
Obtained catalyst carries out one-step method from syngas reaction for preparing light olefins under certain condition, and experimental result is listed in table 1.
【Embodiment 2】
The cocoanut active charcoal weighing 100.0 gram of 60 ~ 80 mesh carries out dust technology and deionized water carrying out washing treatment, dry at 120 DEG C
It is stand-by that dry 4h makes carrier H；By 303.6 grams of Fe(NO3)39H2Os, 3.6 grams of cabaltous nitrate hexahydrates, 8.2 grams of strontium nitrates, 4.9 gram four
Hydration ammonium heptamolybdate, 2.3 gram of five nitric hydrate erbium, are dissolved in 20.0 grams of deionized waters and make mixed solution I；In vacuum
Under conditions of 80kPa, above-mentioned mixed solution I be impregnated on 30.0 grams of coconut activated high-area carbon H having prepared to obtain catalyst
Precursor J；The catalyst precarsor J having impregnated is dried under the conditions of 120 DEG C, then carries out roasting, 600 DEG C of sintering temperature, during roasting
Between 3h, that is, obtain the catalyst of required one-step method from syngas producing light olefins.Prepared catalyst by weight percentage, wraps
Containing following components：60% Fe2O3, 1% Co3O4, 4% SrO, 4% MoO3, 1% Er2O3, 30% C；Obtained catalyst is one
Carry out one-step method from syngas reaction for preparing light olefins, experimental result is listed in table 1 under fixed condition.
【Embodiment 3】
The cocoanut active charcoal weighing 100.0 gram of 60 ~ 80 mesh carries out dust technology and deionized water carrying out washing treatment, dry at 120 DEG C
It is stand-by that dry 4h makes carrier H；By 25.3 grams of Fe(NO3)39H2Os, 3.6 grams of cabaltous nitrate hexahydrates, 8.2 grams of strontium nitrates, 4.9 gram four
Hydration ammonium heptamolybdate, 2.3 gram of five nitric hydrate erbium, are dissolved in 35.0 grams of deionized waters and make mixed solution I；In vacuum
Under conditions of 80kPa, above-mentioned mixed solution I be impregnated on 85.0 grams of coconut activated high-area carbon H having prepared to obtain catalyst
Precursor J；The catalyst precarsor J having impregnated is dried under the conditions of 120 DEG C, then carries out roasting, 600 DEG C of sintering temperature, during roasting
Between 3h, that is, obtain the catalyst of required one-step method from syngas producing light olefins.Prepared catalyst by weight percentage, wraps
Containing following components：5% Fe2O3, 1% Co3O4, 4% SrO, 4% MoO3, 1% Er2O3, 85% C；Obtained catalyst is certain
Under the conditions of carry out one-step method from syngas reaction for preparing light olefins, experimental result is listed in table 1.
【Embodiment 4】
The cocoanut active charcoal weighing 100.0 gram of 60 ~ 80 mesh carries out dust technology and deionized water carrying out washing treatment, dry at 120 DEG C
It is stand-by that dry 4h makes carrier H；By 50.6 grams of Fe(NO3)39H2Os, 36.3 grams of cabaltous nitrate hexahydrates, 40.8 grams of strontium nitrates, 24.5 grams
Four hydration ammonium heptamolybdates, 23.2 gram of five nitric hydrate erbium, are dissolved in 35.0 grams of deionized waters and make mixed solution I；In vacuum
Under conditions of 80kPa, above-mentioned mixed solution I be impregnated on 30.0 grams of coconut activated high-area carbon H having prepared to obtain catalyst
Precursor J；The catalyst precarsor J having impregnated is dried under the conditions of 120 DEG C, then carries out roasting, 600 DEG C of sintering temperature, during roasting
Between 3h, that is, obtain the catalyst of required one-step method from syngas producing light olefins.Prepared catalyst by weight percentage, wraps
Containing following components：10% Fe2O3, 10% Co3O4, 20% SrO, 20% MoO3, 10% Er2O3, 30% C；Obtained catalyst
Carry out one-step method from syngas reaction for preparing light olefins under certain condition, experimental result is listed in table 1.
【Embodiment 5】
The cocoanut active charcoal weighing 100.0 gram of 60 ~ 80 mesh carries out dust technology and deionized water carrying out washing treatment, dry at 120 DEG C
It is stand-by that dry 4h makes carrier H；By 253.0 grams of Fe(NO3)39H2Os, 18.1 grams of cabaltous nitrate hexahydrates, 10.2 grams of strontium nitrates, 6.1 grams
Four hydration ammonium heptamolybdates, 11.6 gram of five nitric hydrate erbium, are dissolved in 35.0 grams of deionized waters and make mixed solution I；In vacuum
Under conditions of 80kPa, above-mentioned mixed solution I be impregnated on 30.0 grams of coconut activated high-area carbon H having prepared to obtain catalyst
Precursor J；The catalyst precarsor J having impregnated is dried under the conditions of 120 DEG C, then carries out roasting, 600 DEG C of sintering temperature, during roasting
Between 3h, that is, obtain the catalyst of required one-step method from syngas producing light olefins.Prepared catalyst by weight percentage, wraps
Containing following components：50% Fe2O3, 5% Co3O4, 5% SrO, 5% MoO3, 5% Er2O3, 30% C；Obtained catalyst is one
Carry out one-step method from syngas reaction for preparing light olefins, experimental result is listed in table 1 under fixed condition.
【Embodiment 6】
The cocoanut active charcoal weighing 100.0 gram of 60 ~ 80 mesh carries out dust technology and deionized water carrying out washing treatment, dry at 120 DEG C
It is stand-by that dry 4h makes carrier H；By 101.2 grams of Fe(NO3)39H2Os, 10.9 grams of cabaltous nitrate hexahydrates, 30.6 grams of strontium nitrates, 18.4
Grams four hydration ammonium heptamolybdates, 16.2 gram of five nitric hydrate erbium, are dissolved in 35.0 grams of deionized waters and make mixed solution I；In vacuum
Under conditions of degree 80kPa, above-mentioned mixed solution I be impregnated in and must be catalyzed on 40.0 grams of coconut activated high-area carbon H having prepared
Agent precursor J；The catalyst precarsor J having impregnated is dried under the conditions of 120 DEG C, then carries out roasting, 600 DEG C of sintering temperature, roasting
Time 3h, that is, obtain the catalyst of required one-step method from syngas producing light olefins.Prepared catalyst by weight percentage,
Comprise following components：20% Fe2O3, 3% Co3O4, 15% SrO, 15% MoO3, 7% Er2O3, 40% C；Obtained catalyst
Carry out one-step method from syngas reaction for preparing light olefins under certain condition, experimental result is listed in table 1.
【Embodiment 7】
The cocoanut active charcoal weighing 100.0 gram of 60 ~ 80 mesh carries out dust technology and deionized water carrying out washing treatment, dry at 120 DEG C
It is stand-by that dry 4h makes carrier H；By 91.1 grams of Fe(NO3)39H2Os, 3.6 grams of cabaltous nitrate hexahydrates, 10.2 grams of strontium nitrates, 6.1 gram four
Hydration ammonium heptamolybdate, 2.3 gram of five nitric hydrate erbium, are dissolved in 35.0 grams of deionized waters and make mixed solution I；In vacuum
Under conditions of 80kPa, above-mentioned mixed solution I be impregnated on 70.0 grams of coconut activated high-area carbon H having prepared to obtain catalyst
Precursor J；The catalyst precarsor J having impregnated is dried under the conditions of 120 DEG C, then carries out roasting, 600 DEG C of sintering temperature, during roasting
Between 3h, that is, obtain the catalyst of required one-step method from syngas producing light olefins.Prepared catalyst by weight percentage, wraps
Containing following components：18% Fe2O3, 1% Co3O4, 5% SrO, 5% MoO3, 1% Er2O3, 70% C；Obtained catalyst is one
Carry out one-step method from syngas reaction for preparing light olefins, experimental result is listed in table 1 under fixed condition.
【Embodiment 8】
The cocoanut active charcoal weighing 100.0 gram of 60 ~ 80 mesh carries out dust technology and deionized water carrying out washing treatment, dry at 120 DEG C
It is stand-by that dry 4h makes carrier H；By 96.1 grams of Fe(NO3)39H2Os, 10.9 grams of cabaltous nitrate hexahydrates, 18.4 grams of strontium nitrates, 12.3 grams
Four hydration ammonium heptamolybdates, 7.0 gram of five nitric hydrate erbium, 2.1 grams of potassium nitrate, are dissolved in 35.0 grams of deionized waters and make mixed solution
I；Under conditions of vacuum 80kPa, above-mentioned mixed solution I be impregnated in 55.0 grams of coconut activated high-area carbon H having prepared
Go up to obtain catalyst precarsor J；The catalyst precarsor J having impregnated is dried under the conditions of 120 DEG C, then carries out roasting, sintering temperature 600
DEG C, roasting time 3h, that is, obtain the catalyst of required one-step method from syngas producing light olefins.Prepared catalyst is with weight hundred
Divide than meter, comprise following components：19% Fe2O3, 3% Co3O4, 9% SrO, 10% MoO3, 3% Er2O3, 1%K2O, 55% C；Made
The catalyst obtaining carries out one-step method from syngas reaction for preparing light olefins under certain condition, and experimental result is listed in table 1.
【Embodiment 9】
The cocoanut active charcoal weighing 100.0 gram of 60 ~ 80 mesh carries out dust technology and deionized water carrying out washing treatment, dry at 120 DEG C
It is stand-by that dry 4h makes carrier H；By 101.2 grams of Fe(NO3)39H2Os, 10.9 grams of cabaltous nitrate hexahydrates, 57.3 gram of six nitric hydrate
Magnesium, 12.3 gram of four hydration ammonium heptamolybdate, 7.0 gram of five nitric hydrate erbium, are dissolved in 35.0 grams of deionized waters and make mixed solution I；
Under conditions of vacuum 80kPa, above-mentioned mixed solution I be impregnated on 55.0 grams of coconut activated high-area carbon H having prepared
Obtain catalyst precarsor J；The catalyst precarsor J having impregnated is dried under the conditions of 120 DEG C, then carries out roasting, sintering temperature 600
DEG C, roasting time 3h, that is, obtain the catalyst of required one-step method from syngas producing light olefins.Prepared catalyst is with weight hundred
Divide than meter, comprise following components：20% Fe2O3, 3% Co3O4, 9% MgO, 10% MoO3, 3% Er2O3, 55% C；Obtained
Catalyst carries out one-step method from syngas reaction for preparing light olefins under certain condition, and experimental result is listed in table 1.
【Embodiment 10】
The cocoanut active charcoal weighing 100.0 gram of 60 ~ 80 mesh carries out dust technology and deionized water carrying out washing treatment, dry at 120 DEG C
It is stand-by that dry 4h makes carrier H；By 101.2 grams of Fe(NO3)39H2Os, 10.9 grams of cabaltous nitrate hexahydrates, 18.4 grams of strontium nitrates, 34.8
Gram five nitric hydrate zirconiums, 7.0 gram of five nitric hydrate erbium, are dissolved in 35.0 grams of deionized waters and make mixed solution I；In vacuum
Under conditions of 80kPa, above-mentioned mixed solution I be impregnated on 55.0 grams of coconut activated high-area carbon H having prepared to obtain catalyst
Precursor J；The catalyst precarsor J having impregnated is dried under the conditions of 120 DEG C, then carries out roasting, 600 DEG C of sintering temperature, during roasting
Between 3h, that is, obtain the catalyst of required one-step method from syngas producing light olefins.Prepared catalyst by weight percentage, wraps
Containing following components：20% Fe2O3, 3% Co3O4, 9% SrO, 10% ZrO2, 3% Er2O3, 55% C；Obtained catalyst is one
Carry out one-step method from syngas reaction for preparing light olefins, experimental result is listed in table 1 under fixed condition.
【Embodiment 11】
The cocoanut active charcoal weighing 100.0 gram of 60 ~ 80 mesh carries out dust technology and deionized water carrying out washing treatment, dry at 120 DEG C
It is stand-by that dry 4h makes carrier H；By 101.2 grams of Fe(NO3)39H2Os, 10.9 grams of cabaltous nitrate hexahydrates, 57.3 gram of six nitric hydrate
Magnesium, 34.8 gram of five nitric hydrate zirconium, 7.0 gram of five nitric hydrate erbium, are dissolved in 35.0 grams of deionized waters and make mixed solution I；?
Under conditions of vacuum 80kPa, above-mentioned mixed solution I be impregnated on 55.0 grams of coconut activated high-area carbon H having prepared
Catalyst precarsor J；The catalyst precarsor J having impregnated is dried under the conditions of 120 DEG C, then carries out roasting, 600 DEG C of sintering temperature,
Roasting time 3h, that is, obtain the catalyst of required one-step method from syngas producing light olefins.Prepared catalyst is with weight percent
Ratio meter, comprises following components：20% Fe2O3, 3% Co3O4, 9% MgO, 10% ZrO2, 3% Er2O3, 55% C；Obtained urges
Agent carries out one-step method from syngas reaction for preparing light olefins under certain condition, and experimental result is listed in table 1.
【Embodiment 12】
The cocoanut active charcoal weighing 100.0 gram of 60 ~ 80 mesh carries out dust technology and deionized water carrying out washing treatment, dry at 120 DEG C
It is stand-by that dry 4h makes carrier H；By 101.2 grams of Fe(NO3)39H2Os, 10.9 grams of cabaltous nitrate hexahydrates, 18.4 grams of strontium nitrates, 12.3
Grams four hydration ammonium heptamolybdates, 7.0 gram of five nitric hydrate erbium, are dissolved in 35.0 grams of deionized waters and make mixed solution I；In vacuum
Under conditions of 80kPa, above-mentioned mixed solution I be impregnated on 55.0 grams of coconut activated high-area carbon H having prepared to obtain catalyst
Precursor J；The catalyst precarsor J having impregnated is dried under the conditions of 120 DEG C, then carries out roasting, 450 DEG C of sintering temperature, during roasting
Between 6h, that is, obtain the catalyst of required one-step method from syngas producing light olefins.Prepared catalyst by weight percentage, wraps
Containing following components：20% Fe2O3, 3% Co3O4, 9% SrO, 10% MoO3, 3% Er2O3, 55% C；Obtained catalyst is one
Carry out one-step method from syngas reaction for preparing light olefins, experimental result is listed in table 1 under fixed condition.
【Embodiment 13】
The cocoanut active charcoal weighing 100.0 gram of 60 ~ 80 mesh carries out dust technology and deionized water carrying out washing treatment, dry at 120 DEG C
It is stand-by that dry 4h makes carrier H；By 101.2 grams of Fe(NO3)39H2Os, 10.9 grams of cabaltous nitrate hexahydrates, 18.4 grams of strontium nitrates, 12.3
Grams four hydration ammonium heptamolybdates, 7.0 gram of five nitric hydrate erbium, are dissolved in 35.0 grams of deionized waters and make mixed solution I；In vacuum
Under conditions of 80kPa, above-mentioned mixed solution I be impregnated on 60.0 grams of coconut activated high-area carbon H having prepared to obtain catalyst
Precursor J；The catalyst precarsor J having impregnated is dried under the conditions of 120 DEG C, then carries out roasting, 700 DEG C of sintering temperature, during roasting
Between 1h, that is, obtain the catalyst of required one-step method from syngas producing light olefins.Prepared catalyst by weight percentage, wraps
Containing following components：20% Fe2O3, 3% Co3O4, 9% SrO, 10% MoO3, 3% Er2O3, 55% C；Obtained catalyst is one
Carry out one-step method from syngas reaction for preparing light olefins, experimental result is listed in table 1 under fixed condition.
【Embodiment 14】
The catalyst that Example 1 is obtained, other are constant, only change reaction condition, carry out one-step method from syngas low-carbon (LC)
Alkene, experimental result is listed in table 2.
【Comparative example 1】
The cocoanut active charcoal weighing 100.0 gram of 60 ~ 80 mesh carries out dust technology and deionized water carrying out washing treatment, dry at 120 DEG C
It is stand-by that dry 4h makes carrier H；By 115.9 grams of Fe(NO3)39H2Os, 0.4 gram of cabaltous nitrate hexahydrate, 18.4 grams of strontium nitrates, 12.3 grams
Four hydration ammonium heptamolybdates, 7.0 gram of five nitric hydrate erbium, are dissolved in 35.0 grams of deionized waters and make mixed solution I；In vacuum
Under conditions of 80kPa, above-mentioned mixed solution I be impregnated on 55.0 grams of coconut activated high-area carbon H having prepared to obtain catalyst
Precursor J；The catalyst precarsor J having impregnated is dried under the conditions of 120 DEG C, then carries out roasting, 600 DEG C of sintering temperature, during roasting
Between 3h, that is, obtain the catalyst of required one-step method from syngas producing light olefins.Prepared catalyst by weight percentage, wraps
Containing following components：22.9% Fe2O3, 0.1% Co3O4, 9% SrO, 10% MoO3, 3% Er2O3, 55% C；Obtained catalyst
Carry out one-step method from syngas reaction for preparing light olefins under certain condition, experimental result is listed in table 1.
【Comparative example 2】
The cocoanut active charcoal weighing 100.0 gram of 60 ~ 80 mesh carries out dust technology and deionized water carrying out washing treatment, dry at 120 DEG C
It is stand-by that dry 4h makes carrier H；By 101.2 grams of Fe(NO3)39H2Os, 43.5 grams of cabaltous nitrate hexahydrates, 18.4 grams of strontium nitrates, 12.3
Grams four hydration ammonium heptamolybdates, 7.0 gram of five nitric hydrate erbium, are dissolved in 35.0 grams of deionized waters and make mixed solution I；In vacuum
Under conditions of 80kPa, above-mentioned mixed solution I be impregnated on 46.0 grams of coconut activated high-area carbon H having prepared to obtain catalyst
Precursor J；The catalyst precarsor J having impregnated is dried under the conditions of 120 DEG C, then carries out roasting, 600 DEG C of sintering temperature, during roasting
Between 3h, that is, obtain the catalyst of required one-step method from syngas producing light olefins.Prepared catalyst by weight percentage, wraps
Containing following components：20% Fe2O3, 12% Co3O4, 9% SrO, 10% MoO3, 3% Er2O3, 46% C；Obtained catalyst exists
Carry out one-step method from syngas reaction for preparing light olefins, experimental result is listed in table 1 under certain condition.
【Comparative example 3】
The cocoanut active charcoal weighing 100.0 gram of 60 ~ 80 mesh carries out dust technology and deionized water carrying out washing treatment, dry at 120 DEG C
It is stand-by that dry 4h makes carrier H；By 115.9 grams of Fe(NO3)39H2Os, 10.9 grams of cabaltous nitrate hexahydrates, 18.4 grams of strontium nitrates, 12.3
Grams four hydration ammonium heptamolybdates, 0.23 gram of five nitric hydrate erbium, are dissolved in 35.0 grams of deionized waters and make mixed solution I；In vacuum
Under conditions of degree 80kPa, above-mentioned mixed solution I be impregnated in and must be catalyzed on 55.0 grams of coconut activated high-area carbon H having prepared
Agent precursor J；The catalyst precarsor J having impregnated is dried under the conditions of 120 DEG C, then carries out roasting, 600 DEG C of sintering temperature, roasting
Time 3h, that is, obtain the catalyst of required one-step method from syngas producing light olefins.Prepared catalyst by weight percentage,
Comprise following components：22.9% Fe2O3, 3% Co3O4, 9% SrO, 10% MoO3, 0.1% Er2O3, 55% C；Obtained catalysis
Agent carries out one-step method from syngas reaction for preparing light olefins under certain condition, and experimental result is listed in table 1.
【Comparative example 4】
The cocoanut active charcoal weighing 100.0 gram of 60 ~ 80 mesh carries out dust technology and deionized water carrying out washing treatment, dry at 120 DEG C
It is stand-by that dry 4h makes carrier H；By 101.2 grams of Fe(NO3)39H2Os, 10.9 grams of cabaltous nitrate hexahydrates, 18.4 grams of strontium nitrates, 12.3
Grams four hydration ammonium heptamolybdates, 27.8 gram of five nitric hydrate erbium, are dissolved in 35.0 grams of deionized waters and make mixed solution I；In vacuum
Under conditions of degree 80kPa, above-mentioned mixed solution I be impregnated in and must be catalyzed on 46.0 grams of coconut activated high-area carbon H having prepared
Agent precursor J；The catalyst precarsor J having impregnated is dried under the conditions of 120 DEG C, then carries out roasting, 600 DEG C of sintering temperature, roasting
Time 3h, that is, obtain the catalyst of required one-step method from syngas producing light olefins.Prepared catalyst by weight percentage,
Comprise following components：20% Fe2O3, 3% Co3O4, 9% SrO, 10% MoO3, 12% Er2O3, 46% C；Obtained catalyst
Carry out one-step method from syngas reaction for preparing light olefins under certain condition, experimental result is listed in table 1.
Above-described embodiment with the reducing condition of comparative example is：
450 DEG C of temperature
Pressure normal pressure
Loaded catalyst 3 ml
Catalyst loading 1000 hours-1
Also Primordial Qi H2
8 hours recovery times
Reaction condition is：
8 millimeters of fixed bed reactors of φ
360 DEG C of reaction temperature
Reaction pressure 1.8MPa
Loaded catalyst 3 ml
Catalyst loading 1000 hours-1
Raw material proportioning (mole) H2/ CO=1.5/1
Table 1
Table 2
* the appreciation condition of change compared with the condition described in table 1.
Claims (10)
1. a kind of catalyst for one-step method from syngas producing light olefins, includes following components by weight percentage：
A) oxide of 5～60% iron；
B) oxide of 1～10% cobalt；
C) 4～20% at least one oxide in strontium and magnesium；
D) 4～20% at least one oxide in molybdenum and zirconium；
E) oxide of 1～10% erbium；
F) 30～85% coconut activated high-area carbon.
2. the catalyst for one-step method from syngas producing light olefins according to claim 1 is it is characterised in that described
In catalyst, the oxide of iron is di-iron trioxide, and in terms of catalyst weight percent, content is 10～50%.
3. the catalyst for one-step method from syngas producing light olefins according to claim 1 is it is characterised in that described
In catalyst, the oxide of cobalt is cobaltosic oxide, and in terms of catalyst weight percent, content is 1～5%.
4. the catalyst for one-step method from syngas producing light olefins according to claim 1 is it is characterised in that described
In catalyst the oxide of strontium and magnesium be respectively strontium oxide strontia and magnesia, in terms of catalyst weight percent, content be 5～
15%.
5. the catalyst for one-step method from syngas producing light olefins according to claim 1 is it is characterised in that described
In catalyst the oxide of molybdenum and zirconium be respectively molybdenum oxide and zirconium oxide, in terms of catalyst weight percent, content be 5～
15%.
6. the catalyst for one-step method from syngas producing light olefins according to claim 1 is it is characterised in that described
In catalyst, the oxide of erbium is erbium oxide, and in terms of catalyst weight percent, content is 1～5%.
7. the catalyst for one-step method from syngas producing light olefins according to claim 1 is it is characterised in that described
Coconut activated high-area carbon in catalyst, in terms of catalyst weight percent, content is 40～70%.
8. the preparation method of the catalyst for one-step method from syngas producing light olefins described in any one of claim 1～7, bag
Include following steps：
(1) coconut activated high-area carbon water washed for pickling is dried process, makes carrier H stand-by；
(2) by molysite, cobalt salt, strontium salt or magnesium salts, molybdenum salt or zirconates, and erbium salt, it is dissolved in water deionized water that to make mixing molten
Liquid I；
(3) under the conditions of vacuum 1～80kPa, above-mentioned mixed solution I be impregnated on the carrier H handling well in (1) step
Catalyst precarsor J；
(4) by catalyst precarsor J, roasting after drying, obtain required catalyst.
9. the preparation method for one-step method from syngas producing light olefins catalyst according to claim 8, its feature exists
Sintering temperature in catalyst precarsor is 450～700 DEG C, roasting time 1.0～6.0 hours.
10. a kind of method of one-step method from syngas producing light olefins, with synthesis gas as raw material, H2Mol ratio with CO is 1～3,
Reaction temperature is 250～400 DEG C, and reaction pressure is 1.0～3.0Mpa, and feed gas volume air speed is 500～5000h-1Condition
Under, unstripped gas is generated with the catalyst haptoreaction described in any one of claim 1～7 and contains C2～C4Alkene.
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| CN105498798A (en) * | 2015-12-11 | 2016-04-20 | 中国科学院上海高等研究院 | Catalyst for directly converting synthesis gas into long-chain alkene by one-step method |
| CN106345514B (en) * | 2016-07-29 | 2018-11-13 | 厦门大学 | A kind of catalyst and preparation method thereof of one step of synthesis gas conversion producing light olefins |
| CN109092317B (en) * | 2017-06-21 | 2021-03-26 | 中国石油化工股份有限公司 | Catalyst system for preparing low-carbon olefin by directly synthesizing gas |
| CN109304216B (en) * | 2017-07-28 | 2021-06-22 | 中国石油化工股份有限公司 | Catalyst for producing low-carbon olefin by synthesis gas one-step method |
| CN109651033B (en) * | 2017-10-10 | 2021-08-03 | 中国石油化工股份有限公司 | Method for preparing low-carbon olefin by fixed bed |
| CN110639486B (en) * | 2018-06-27 | 2022-07-12 | 中国石油化工股份有限公司 | Catalyst for preparing low-carbon olefin from synthesis gas and application of catalyst in preparation of low-carbon olefin from synthesis gas |
| CN109012676B (en) * | 2018-08-16 | 2021-07-20 | 山东东岳化工有限公司 | Catalyst for preparing hydrofluoroolefin by removing HF from hydrofluoroalkane gas phase, and preparation method and application thereof |
| CN115518647B (en) * | 2021-06-24 | 2023-08-08 | 中国石油化工股份有限公司 | Catalyst for producing low-carbon olefin by fixed bed synthesis gas and preparation method and application thereof |
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